US4877914A

US4877914A - Process for preparing polyalkyl tetrahydronaphthalenes

Info

Publication number: US4877914A
Application number: US07/303,419
Authority: US
Inventors: Walter C. Frank
Original assignee: Union Camp Corp
Current assignee: Union Camp Corp
Priority date: 1989-01-27
Filing date: 1989-01-27
Publication date: 1989-10-31
Anticipated expiration: 2009-01-27

Abstract

A process is disclosed for the production of polyalkyl tetrahydronaphthalenes is disclosed wherein a cyclialkylation reaction between an olefinic compound of the general Formula ##STR1## wherein R⁴, R⁵ and R⁶ are independently defined and each represents a substituent which does not interfere substantially in Friedel-Crafts type reactions and R⁵ and R⁶ are other than H, and a substituted benzene compound is carried out in the presence of an alkyl halide, a Lewis acid and a phase transfer agent. The subject process produces the desired compounds in a surprisingly high yield, with a surprisingly high selectivity to the desired product, and at a relatively high rate of reaction, using better, more convenient, or less expensive process methodology than many processes known heretofore.

Description

BACKGROUND OF THE INVENTION

The present invention relates to an improved process for the production of polyalkyl tetrahydronaphthalenes, particularly 1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene, the latter compound referred to herein as "HMT".

HMT and other alkyl-substituted tetrahydronaphthalenes are of significant importance to the perfumery as well as other industries. By conventional acylation processes, HMT, for example, can be converted to 7-acteyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene, a well known musk perfume. Because of their clean must fragrance and ability to retain that fragrance over long periods of time, these HMT derivatives are of great commercial value as synthetic musk perfume substitutes for the expensive, natural musk perfumes of the macrocyclic ketone series. Consequently, various synthetic methods have been proposed for the production of HMT, as well as other related intermediates of HMT useful in the perfumery or other industries.

For example, Sato et al., U.S. Pat. No. 4,284,818 entitled "Process for Preparing Hexamethyltetrahydronaphthalenes," describes a process for producing HMT comprising reacting para-cymene with a 2,3-dimethylbutene using a catalytic amount of anhydrous aluminum halide in the presence of a secondary alkyl halide, tertiary alkyl halide, propargyl halide or allyl halide. It is noted that both the 2,3-dimethyl-1-butene and 2,3-dimethyl-2-butene can be employed as the 2,3-dimethylbutene reagent, however, 2,3-dimethyl-1-butene is said to yield better results. The reaction is generally carried out using a solvent, such solvents including aliphatic hydrocarbons, halogenated aromatic hydrocarbons, and halogenated aliphatic hydrocarbons.

Wood et al., U.S. Pat. No. 3,856,875 entitled "Process for Producing 1,1,3,4,4,6-Hexamethyl-1,2,3,4-Tetrahydronapthalene [sic] (HMT)," discusses a process for the preparation of HMT wherein an equivalent or excess amount of para-cymene is reacted with a substantially equal molar solution of neohexene (3,3-dimethyl-1-butene) and a tertiary alkyl halide in the presence of an effective amount of an anhydrous aluminum halide catalyst suspended in a reaction-compatible solvent. Although any tertiary alkyl halide can be employed in the disclosed process, tertiary butyl chloride, tertiary amyl chloride and 2,5-dichloro-2,5-dimethylhexane are noted as preferred. The process is described as having a solvent dependency, with the satisfactory solvents being ethylene dichloride, chloroform, methylene dichloride, 1,1,2,2-tetrachloroethane, 1,2-dichloroethylene, 1,2,3-trichloropropane, 1,1,2-trichloroethane, monochlorobenzene, fluorobenzene, ortho-dichlorobenzene, and para-xylene. Numerous solvents are stated to be unsatisfactory for use in the disclosed process, such solvents including nitromethane, benzene, nitrobenzene, para-cymene, n-hexane, 1,2,2-trichloroethylene, carbon tetrachloride, 1,1,1-trichloroethane, carbon disulfide, 1,1,2,2,2-pentachloroethane, 1,2-dichloropropane, 1,1-dichloroethylene, and 1,1-dichloroethane. These unsatisfactory solvents are said to yield substantially poorer results.

Kahn, U.S. Pat. No. 3,379,785 entitled "Process for Preparing Polyalkyltetrahydronaphthalenes," relates to a process for preparing polyalkyl tetrahydronaphthalenes, and more specifically, a process for preparing HMT. The process involves the reaction of a substituted styrene and a 2,3-dimethylbutene, said reaction being carried out at elevated temperatures and in the presence of a cation exchange resin. The 2,3-dimethylbutene reactant employed is disclosed as comprising either 2,3-dimethyl-1-butene, 2,3-dimethyl-2-butene, or mixtures thereof. The preferably employed solvent comprises an aromatic hydrocarbon, such as, for example, benzene, toluene, ethylbenzene, or a xylene.

Wood, U.S. Pat. No. 3,246,044 entitled "Process for Making 1,1,3,4,4,6-Hexamethyl-1,2,3,4-Tetrahydronaphthalene," discloses a process for preparing HMT which includes reacting an alpha,para-dimethylstyrene derivative such as dimethyl-para-tolyl-carbinyl halide, and neohexene in the presence of a catalyst such as aluminum chloride, aluminum bromide and ferric chloride,e or other Friedel-Crafts catalysts, at low temperatures. Suitable solvents are listed as ethylene dichloride or carbon tetrachloride, or other inert chlorinated hydrocarbon solvents. It is noted that other solvents such as nitrobenzene and nitromethane, may be used, but the yield of desired product is indicated as generally being lower when such solvents are employed.

Cobb, U.S. Pat. No. 4,551,573 entitled "Alkylation of Aromatic Compounds," discloses a process for the alkylation of aromatic compounds with olefinic compounds in the presence of a catalyst consisting essentially of aluminum halide and elemental iodine. Examples of aromatic compounds described as suitable for use in the process include para-cymene, and olefinic compounds discussed include 2,3-dimethyl-2-butene, isobutylene and neohexene. A mixture of olefinic compounds can also be employed, in which case it is noted that one of the olefins may function as a sacrificial agent. The products of the alkylation reaction described include indanes and HMT-type compounds.

Japanese Patent Publication SHO 57-40420 discusses a method of making HMT characterized by reaction para-cymene and neohexene in the presence of anhydrous aluminum halide as catalyst. Suitable anhydrous aluminum halides are said to include aluminum chloride. The reaction is generally carried in a solvent, however, it is noted that it is possible to conduct the reaction without any additional solvent using excess para-cymene. Examples of suitable solvents are methylene chloride, ethylene chloride, chloroform and other inactive fatty hydrocarbon halides. Other solvents such as aromatic hydrocarbon halides, fatty hydrocarbons, aromatic hydrocarbons, etc., can be used, but it is noted that the use of such solvents generally lowers the yield of the desired end product.

Suzukamo et al., U.S. Pat. No. 4,767,882 entitled "Tetrahydronaphthalene Derivatives and Their Production," discloses a process for preparing a tetrahydronaphthalene derivative in an optically active state which comprises reacting a benzene compound and a pyrocine compound in the presence of a Lewis acid, or, alternatively, reacting the benzene with the pyrocine compound in the presence of an acid catalyst followed by treatment of the resultant product with the Lewis acid.

These prior art processes suffer from various drawbacks, including low conversion of reactants, poor selectivity to the desired products, sluggish reaction rates, unacceptably low temperature requirements, unsafe solvent system, or oxygen sensitivity. New and/or better processes are needed. The present invention is directed to this important end.

SUMMARY OF THE INVENTION

The present invention provides a process for the production of polyalkyl tetrahydronaphthalenes wherein a cyclialkylation reaction between an olefinic compound of the general Formula ##STR2## and a substituted benzene compound is carried out in the presence of an alkyl halide, a Lewis acid and a phase transfer agent. The subject process produces the desired compounds in a surprisingly high yield, with a surprisingly high selectivity to the desired product, and at a surprisingly high rate of reaction, using better, more convenient or less expensive process methodology than many processes known heretofore.

Specifically, the present invention pertains to a process for producing polyalkyl tetrahydronaphthalenes, such as those represented by the Formulas ##STR3## comprising reacting a partially substituted benzene compound, wherein said benzene compound is substituted with two or more substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction said substituents including at least one secondary alkyl group having only one alpha-hydrogen, and wherein said benzene compound is unsubstituted in at least one position adjacent to said secondary alkyl group, such as those compounds of the Formulas ##STR4## with an olefinic compound of the Formula ##STR5## in the presence of an alkyl halide, a Lewis acid, and a phase transfer agent. In the above Formulas, R¹, R², R³, R⁴, R⁵ and R⁶ are, independently, substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction, provided that R¹, R², R³, R⁵ and R⁶ are each other than H.

Using the foregoing process, one is able to produce a variety of alkyl-substituted tetrahydronaphthalene compounds for use as chemical intermediates and/or chemical products, particularly intermediates such as HMT, which is a compound of extreme importance to the fragrance industry.

DETAILED DESCRIPTION OF THE INVENTION

As noted above, the present invention pertains to a novel and particularly useful process for the production of polyalkyl tetrahydronaphthalenes, including, but not limited to, those of Formulas I, II or III: ##STR6##

In the above Formulas, R¹, R², R³, R⁴, R⁵ and R⁶ are defined, independently, as substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction, provided that R¹, R², R³, R⁵ and R⁶ are each other than H. Suitable R¹, R², R³, R⁴, R⁵ and R⁶ substituents will be readily apparent to those skilled in the art of Friedel-Crafts-type alkylation reactions. Such alkylation reactions and non-interfering substituents are discussed, for example, in George A. Olah, Friedel-Crafts and Related Reactions, Vols. 1 and 2 (Interscience Publishers, John Wiley and Sons, 1964) (hereinafter referred to as "Friedel-Crafts Reactions"), as well as in other journal and textbook references. The disclosures of Friedel-Crafts Reactions are incorporated herein by reference. Examples of suitable substituents include those wherein R⁴ is H, or a C₁ -C₃₀ straight chain, branched or cyclical alkyl, and R¹, R², R³, R⁵ and R⁶, independently, are a C₁ -C₃₀ straight chain, branched or cyclical alkyl. The alkyl is preferably a C₁ -C₂₀, more preferably a C₁ -C₁₀, and most preferably a C₁ -C₅, alkyl. Preferably, the alkyl is a straight chain or branched alkyl. In a generally preferred embodiment, R¹, R², R³, R⁴, R⁵ and R⁶, independently, are a C₁ -C₅ straight chain or branched alkyl.

In a most preferred embodiment, the polyalkyl tetrahydronaphthalenes are of the Formula I. The Formula I compounds are preferably:

1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (that is, HMT, a compound of Formula I wherein R¹, R², R³, R⁵ and R⁶ are each methyl);

6-ethyl-1,1,3,4,4-pentamethyl-1,2,3,4-tetrahydronaphthalene (that is, a compound of Formula I wherein R¹ is ethyl, and R², R³, R⁴, R⁵ and R⁶ are each methyl);

6-tertiary-butyl-1,1,3,4,4-pentamethyl-1,2,3,4- tetrahydronaphthalene (that is, a compound of Formula I wherein R¹ is tertiary butyl, and R², R³, R⁴, R⁵ and R⁶ are each methyl); and

6-n-propyl-1,13,4,4-pentamethyl-1,2,3,4-tetrahydronaphthalene (that is, a compound of Formula I wherein R¹ is n-propyl, and R², R³, R⁴, R⁵ and R⁶ are each methyl).

The compounds of Formulas I, II and III are produced by contacting a partially substituted benzene compound, wherein said benzene compound is substituted with one or more substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction said substituents including at least one secondary alkyl group having only one alpha-hydrogen, and wherein said benzene compound is unsubstituted in at least one position adjacent to said secondary alkyl group, such substituted benzene compounds including, but not limited to, those of the Formulas IV or V ##STR7## with an olefinic compound of the Formula VI ##STR8##

As those skilled in the art would recognize, contacting a benzene compound of Formula IV with an olefinic compound of Formula VI will yield the tetrahydronaphthalene compounds of Formula I. Alternatively, contacting a benzene compound of Formula V with an olefinic compound of Formula VI will yield the tetrahydronaphthalene compounds of Formulas II and III. The Formula I, II, or III compounds may isomerize under the reaction conditions to also form one or more of the other compounds of Formulas I, II, or III. In the above, Formulas IV, V and VI, R¹, R², R³, R⁴, R⁵ and R⁶ are defined, independently, as previously described, that is, as substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction, provided that R¹, R², R³, R⁵ and R⁶, are each other than H. Suitable substituents are discussed in various journal and textbook references, such as Friedel-Crafts Reactions. Suitable substituents include those wherein R⁴ is H, or a C₁ -C₃₀ straight chain, branched or cyclical alkyl, and R¹, R², R³, R⁵ and R⁶, independently, are a C₁ -C₃₀ straight chain, branched or cyclical alkyl. The alkyl is preferably a C₁ -C₂₀, more preferably a C₁ -C₁₀, and most preferably a C₁ -C₅, alkyl. Preferably the alkyl is a straight chain or branched alkyl.

With respect to the benzene compounds of Formulas IV and V, a generally preferred embodiment includes those compounds wherein R¹, R² and R³, independently, are a C₁ -C₅ straight chain or branched alkyl. In a most preferred embodiment, the substituted benzene compounds are of Formula IV. The Formula IV compounds are preferably isopropyl toluene (that is, para-cymene, a compound of Formula IV wherein R¹, R² and R³ are each methyl), 1-ethyl-4-isopropylbenzene (that is, a compound of Formula IV wherein R¹ is ethyl, and R² and R³ are each methyl), 1-n-propyl-4-isopropylbenzene (that is, a compound of Formula IV wherein R¹ is n-propyl, and R² and R³ are each methyl(, and 1-tertiary-butyl-4-isopropylbenzene (that is, a compound of Formula IV wherein R¹ is tertiary-butyl, and R² and R³ are each methyl).

In a generally preferred embodiment, the olefinic compounds of Formula VI include those compounds wherein R⁴ is H or a C₁ -C₅ straight chain or branched alkyl, and R⁵ and R⁶, independently, are a C₁ -C₅ straight chain or branched alkyl. A more preferable embodiment is wherein R⁴ is methyl. Of the formula VI compounds, 2,3-dimethyl-1-butene (a compound of Formula VI wherein R⁴, R⁵ and R⁶ are each methyl) is most preferred. As those skilled in the art would recognize, as an alternative to adding the terminal olefinic compounds of Formula VI to the reaction mixture in carrying out the process of the invention, one may instead add the internal olefinic isomer of those compounds, that is, compounds of the Formula ##STR9## wherein R⁴, R⁵ and R⁶ are as previously described. Such compounds are capable of rearranging by isomerization under the process conditions of the invention to form the Formula VI compounds believed to be required for polyalkyl tetrahydronaphthalene formation. A preferable internal olefinic isomer is 2,3-dimethyl-2-butene.

In accordance with the present invention, the compounds of Formulas IV or V are reacted with compounds of Formula VI in the presence of an alkyl halide, a Lewis acid, and a phase transfer agent.

Suitable alkyl halides include, but are not limited to, secondary alkyl halides, tertiary alkyl halides, propargyl halides and allyl halides. Exemplary secondary alkyl halides include isopropyl chloride, secondary-butyl chloride, secondary-amyl chloride, cyclohexyl chloride, and homologues thereof having fluorine, bromine or iodine atoms substituted for the chlorine atoms, as well as various secondary alkyl dihalides. Examples of tertiary alkyl halides include tertiary-butyl chloride, tertiary-amyl chloride, 2-methyl-2-chloropentane, 3-methyl-3-chloropentane, as well as various other tertiary alkyl dihalides such as 1,8-dichloro-para-menthane, and homologues thereof having fluorine, bromine or iodine atoms substituted for the chlorine atom. Representative propargyl halides include propargyl chloride, 1-chloro-2-butyne, 1-chloro-2-pentyne, and homologues thereof having fluorine, bromine or iodine atoms substituted for the chlorine atom, as well as various propargyl dihalides. Suitable allyl halides include allyl chloride, 1-chloro-2-butene, 1-chloro-3-methyl-2-butene, 1-chloro-2-pentene, 1-chloro-2-hexene and homologues thereof having fluorine, bromine or iodine atoms substituted for the chlorine atom, as well as various allyl dihalides. Other suitable alkyl halides will be readily apparent to those skilled in the art. Of the foregoing alkyl halides, tertiary alkyl halides, and in particular tertiary-butyl chloride, tertiary-amyl chloride, 2-methyl-2-chloropentane, 3-methyl-3-chloropentane and 1,8-dichloro-para-menthane, are preferred. A most preferred alkyl halide is the tertiary alkyl halide which is tertiary-butylchloride.

Any Lewis acid, that is, any non-protonic compound capable of accepting an electron pair, is suitable for use in the present process. Exemplary Lewis acids include metal halides such as aluminum halides (including aluminum chloride, aluminum bromide, aluminum iodide, monofluorodichloroaluminum, monobromodichloroaluminum and monoiododichloroaluminum), alkyl metal halides and alkyl metals. Alkyl metals and alkyl metal halides suitable for use as Lewis acids in the present process are disclosed, for example, in Kennedy, Joseph P., Carbocationic Polymerization, p. 221 (Wiley-Interscience Publishers (1982)), the disclosures of which are incorporated herein by reference. In the process of the present invention, aluminum halides are preferred. Of the aluminum halides, aluminum chloride and aluminum bromide, particularly aluminum chloride, are most preferred.

Suitable phase transfer agents include oniom salts such as ammonium, phosphonium and sulfonium salts. Other phase transfer agents suitable for use in the present process will be readily apparent to those skilled in the art, once having been made aware of the present disclosure.

Examples of ammonium phase transfer agents include quaternary ammonium halides such as methyltrioctylammonium chloride, methyltrinonylammonium chloride methyltridecylammonium chloride, hexadecyltrihexylammonium bromide, ethyltrioctylammonium bromide, didodecyldimethylammonium chloride, tetraheptylammonium iodide, dioctadecyldimethylammonium chloride, tridecylbenzylammonium chloride, ditricosylmethylammonium chloride, and homologues thereof having chlorine, fluorine, bromine or iodine atoms substituted for the enumerated halide atom. Also suitable for use in the present invention as phase transfer agents are tertiary amine compounds substituted with hydrocarbons, such as trioctyl amine, which, under the conditions of the subject process may be converted to form quaternary ammonium salts.

Exemplary phosphonium phase transfer agents include quaternary phosphonium halides such as tributyldecylphosphonium iodide, triphenyldecylphosphonium iodide, tributylhexadecylphosphonium iodide, and homologues thereof having chlorine, fluorine or bromine atoms substituted for the iodine atom. In addition, trisubstituted phosphine compounds substituted with hydrocarbons, such as tri-n-butyl phosphine, may be converted to quaternary phosphonium salts under the present reaction conditions, and as such, are also suitable for use in the subject process as phase transfer agents.

Representative sulfonium phase transfer agents include ternary sulfonium halides such as lauryldimethylsulfonium iodide, lauryldiethylsulfonium iodide and tri(n-butyl)sulfonium iodide, and homologues thereof having chlorine, fluorine or bromine atoms substituted for the iodine atom. In addition, disubstituted sulfur compounds substituted with hydrocarbons may be converted to ternary sulfonium salts under the present reaction conditions, and as such, are also suitable for use in the subject process as phase transfer agents.

These and other suitable phase transfer agents are described, for example, in U.S. Pat. No. 3,992,432 and in Kondo et al., Synthesis, pp. 403-404 (May 1988), the disclosures of which are incorporated herein by reference.

Preferable phase transfer agents are ammonium or sulfonium salts, particularly quaternary ammonium or ternary sulfonium halides. Most preferred are quaternary ammonium halides, particularly methyltrioctylammonium chloride (referred to herein as "MTOAc"), and a mixture of methyltrioctylammonium chloride and methyltridecylammonium chloride. The latter mixture is marketed under the trademark Adogen-464™, by Sherex Co., located in Dublin, Ohio.

In general, the molar proportions of the reagents employed in the present process can be varied over a relatively wide range. For the best results, however, it is important to maintain a ratio of less than one mole of phase transfer agent per mole of Lewis acid. preferably, the molar ratio is about 0.8 to 1.0, more preferably 0.5 to 1.0, phase transfer agent to Lewis acid. It should be noted that some phase transfer agents sold commercially are sold in an impure form. Such impurities generally comprise water or an alcohol species. Water and alcohol, as well as other impurities, will react adversely with the Lewis acid, thereby lowering the amount of active Lewis acid available for the process of the present invention. Accordingly, where the phase transfer agent added contains such impurities, the amount of Lewis acid should be increased to account for these impurities. In such a situation the ratio of transfer agent to Lewis acid might be about 0.3 to 1.0. Such impure agent-containing mixtures are referred to herein as mixtures in an "impure form".

It is preferable to use a mixture of olefinic compound and alkyl halide wherein these compounds are present in a range of about 1.0 to about 5.0 moles of olefin per mole of halide. More preferably, the olefin and alkyl halide are present in nearly equimolar amounts, that is, about 1.0 to 1.0.

Preferably, the substituted benzene compound is present in a range of about 0.5 to about 10 moles per mole of olefin. More preferably, the substituted benzene compound is present in a range of about 0.5 to about 5.0 per mole of olefin.

In a most preferred embodiment, each of the benzene compound, olefin and alkyl halide are present nearly in equimolar amounts.

The amount of Lewis acid utilized is preferably in the range of about 2% to about 10% by weight of the Lewis acid based on the combined weight of the substituted benzene, olefin and alkyl halide.

The reaction is generally carried out using a solvent, although, if desired, substituted benzene, one of the starting materials, may be employed in large excess in lieu of an additional solvent. Surprisingly, a number of different solvents may be utilized in the present invention, including unhalogenated aliphatic, unhalogenated alicyclic and unhalogenated aromatic hydrocarbon solvents. Such unhalogenated aliphatic, unhalogenated alicyclic and unhalogenated aromatic hydrocarbon solvents are particularly preferred for reasons of safety. Exemplary of these preferred solvents are the aliphatic solvents n-hexane, n-heptane and n-octane, the alicyclic solvent cyclohexane, and the aromatic solvents benzene, toluene, ethylbenzene and xylene. Particularly preferred for reasons of yield, safety and/or process engineering are the unhalogenated aliphatic and unhalogenated alicyclic hydrocarbons. Other suitable solvents are described, for example, in U.S. Pat. Nos. 4,284,818, 3,856,875 and 3,379,785, the disclosures of which are incorporated herein by reference.

The alkylation reaction of the invention can be carried out in any suitable vessel which provides efficient contacting between the Lewis acid, the phase transfer agent and the other reactants. For simplicity, a stirred batch reactor can be employed. Although stirring is recommended to provide efficient contact between reactants, it has been found that with the addition of the phase transfer agent pursuant to the present invention, the Lewis acid is able to solubilize rather quickly, thereby obviating the need for the stringent stirring requirements of many of the art processes utilized to produce HMT. The reaction vessel used should be resistant to the possibly corrosive nature of the catalyst. Glass-lined vessels are suitable for this purpose, as well as other vessel materials well known in the art.

The reagents of the present process may be added in any order, although a preferred mode of carrying out the process is to add the solvent, the Lewis acid and the phase transfer agent first, allow sufficient time for the Lewis acid to become substantially dissolved in the solvent, and then add the remaining reagents. Generally, 15 to 30 minutes are needed for the Lewis acid to become substantially dissolved in the solvent.

Ideally, the reaction is carried out at temperatures ranging from about -30° C. to about 50° C., preferably at temperatures ranging from about -10° C. to about 40 C., and most preferably at temperatures ranging from about 0° C. to about 30° C.

The pressure at which the reaction is carried out is not critical. If the reaction is carried out in a sealed vessel, autogenous pressure is acceptable, although higher or lower pressures, if desired, may be employed. The reaction can also be carried out at atmospheric pressure in an open reaction vessel, in which case the vessel is preferably equipped with a moisture trap to prevent significant exposure of Lewis acid to moisture. The reaction can take place in an oxygen atmosphere, or an inert atmosphere as in the presence of a gas such as nitrogen, argon and the like, the type of atmosphere also not being critical.

Reaction time is generally rather short and is often dictated by the kind of equipment employed. Sufficient time must be provided, however, for thorough contacting of the substituted benzene compound, the olefinic compound, the Lewis acid and the phase transfer agent. Generally the reaction proceeds to completion in about 1 to about 7 hours.

Product can be recovered by first quenching the reaction mixture in cold water or on crushed ice, preferably on ice, and then processing the mixture in the usual manner for Friedel-Crafts reactions to extract the desired alkyl-substituted tetrahydro- naphthalene compounds. Suitable extraction protocol is described, for example, in Friedel-Crafts Reactions. Typically, following quenching and the resultant phase separation, the organic layer is washed an additional time with water to aid in removal of the Lewis acid. One or more additional washings can be carried out with dilute alkali solution to further aid Lewis acid removal. Pure product can then be recovered by subjecting the washed reaction mixture to reduced pressure fractional distillation. The polyalkyl tetrahydronaphthalenes prepared in accordance with the processes of the invention, as hereinbefore indicated, may, for example, be acylated to obtain acylated polyalkyl tetrahydronaphthalenes having very fine, musk-like fragrances, a characteristic which renders them highly valuable for use in the perfumery industry. Such products, acylated or otherwise, may alternatively or additionally have utility in the pharmaceutical and/or agrochemical industries, either as intermediates or as end products, as generally discussed in French Patent Publication No. 2601670, and Cobb, U.S. Patent No. 4,551,573 entitled "Alkylation of Aromatic Compounds." The acylation process may be carried out using conventional methods, such as by reacting the polyalkyl tetrahydronaphthalene with an acyl halide or acid anhydride in the presence of an acid-acting catalyst. Suitable acylation methods are well known in the art and are disclosed, for example, in U.S. Pat. No. 4,284,818. Examples of acylated polyalkyl tetrahydronaphthalenese include 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthaalene, 7-acetyl-1,1,3,4,4-pentamethyl-6-ethyl-1,2,3,4-tetrahydronaphthalene, 7-acetyl-1,1,3,4,4-phentamethyl-6-n-propyl-1,2,3,4-tetrahydronaphthalene, and 7-acetyl-1,1,3,4,4-pentamethyl-6-tettiary-butyl-1,2,3,4-tetrahydronaphthalene.

The present invention is further described in the following Examples. These Examples are not to be construed as limiting the scope of the appended claims.

In each Example, the reaction flasks were equipped with a condenser, mechanical stirrer, addition funnel and thermocouple/ temperature controller connected to an automatic laboratory jack. The flasks were cooled, when necessary, with a dry ice/isopropanol bath. The flask contents were continuously stirred throughout the reaction.

Results were analyzed on both polar and non-polar gas chromatography columns. All gas chromatography analyses were carried out on capillary columns using a weight percent internal standard method of analysis. Structure identifications were assigned based on GCMS fragmentation patterns compared to standards.

Examples 1 and 4 below are provided for comparative purposes only, and do not illustrate processes of the present invention. Specifically, Example 1 was carried out substantially in accordance with the procedures set forth in U.S. Pat. No. 4,284,818. Example 4 is similar to Example 1 except that the reagents were added at twice the rate. Examples 2 and 3 are examples of processes of the present invention.

EXAMPLES Example 1 (Comparative Example)

A 100 ml, four-necked, round bottom flask was charged with cyclohexane (19.10 g) and cooled to 20° C. with a dry ice/ isopropanol bath. Anhydrous aluminum chloride (1.803 g) was added, with stirring, to the cyclohexane. An addition funnel containing a mixture of para-cymene (25.13 g), 2,3-dimethyl-1-butene (7.63 g), and tertiarybutyl chloride (9.52 g) was connected to the flask and the mixture was added over a period of 2.77 hours. At 3 hours, the reaction was quenched with 10 ml of deionized water. The organic layer was washed, in order, with 5% HCl, 10% Na₂ CO₃, and a 50% (that is, half-saturated) brine solution. Each aqueous wash was individually extracted with ethyl ether, and the ether layers combined with the organic phase. The organics were then dried over K₂ CO₃, filtered, and evaporated to give a crude product (29.10 g) containing 28.57 weight % HMT (42.46 % molar y yield of HMT based on the amount of 2,3-dimethyl-1-butene charged). This example was carried out substantially in accordance with the procedure set forth in Sato et al., U.S. Pat. No. 4,284,818 entitled "Process for Preparing Hexamethyltetrahydronaphthalenes," examples #8.

Example 2

A 100 ml, four-necked round bottom flask was charged with cyclohexane (19.10 g). To this was added methyltrioctylammonium chloride (2.735) and anhydrous aluminum chloride (1.803 g). The mixture was cooled to 20° C. and allowed to stir for thirty minutes. A mixture of para-cymene (25.13 g), 2,3-dimethyl-1-butene (7.63 g), and tertiary-butyl chloride (9.52 g) was then added to the flask over a period of 3 hours. When the addition was complete, the reaction was quenched with 15 ml of deionized water. The organic phase was then washed with, in order, 5% HCl, 10% Na₂ CO₃, and a 50% brine solution. Each aqueous wash was individually extracted with ethyl ether, and the ether layers combined with the organic phase. The organics were then dried over K₂ CO₃ and evaporated to yield a crude product (33.78 g) containing 29.22 weight % HMT (50.40 % molar yield of HMT based on the 2,3-dimethyl-1-butene charged). This example as repeated to yield crude product (31.75 g) containing 30.69 weight % HMT (49.76 % molar yield of HMT based on the 2,3-dimethyl-1-butene charged).

Example 2 was carried out in the same manner as Example 1, with the exception that a phase transfer agent, methyltrioctylammonium chloride, was added according to the teachings of this invention. This resulted in a 19% improvement in molar yield of HMT compared with Example 1.

Example 3

This example is a larger scale version of Example 2 where the addition rate of reagents was doubled to ascertain the ability of the catalyst to handle larger amounts of reactants on a per unit time basis.

A 500 ml three-necked round bottom flask was charged with cyclohexane (76.0 g), anhydrous aluminum chloride (7.21 g), and methyltrioctylammonium chloride (10.93 g), and stirred for 0.25 hours at 20° C. A mixture of para-cymene (99.47), 2,3-dimethyl-1-butene (30.21 g, 97% purity), and tertiary-butyl chloride (37.67) was prepared and added to the flask over a period of 1.5 hours. Samples were taken and analyzed every 0.25 hours. Immediately upon completion of the addition the reaction was quenched with water (75 ml) and a sample was taken and analyzed. The remaining product was washed with, in order, 5% aqueous hydrochloric acid, 10% aqueous sodium carbonate, and a 50% brine solution. Each aqueous wash was individually extracted with ethyl ether, and the ether layers combined with the organic phase. The organics were then dried over K₂ CO₃ and evaporated to give a crude product (134.47 g) containing 29.6 weight % HMT (47.5% molar yield based on 2,3-dimethyl-1-butene charged).

The results of the samplings are shown in Table A.

              TABLE A                                                     
______________________________________                                    
Wt % Analysis of Example 4 Samples*                                       
      Time of    Para-          HMT ÷ [Para-                          
Sample                                                                    
      Sample (hrs)                                                        
                 Cymene   HMT   Cymene + HMT]                             
______________________________________                                    
A     0.25       8.51     7.41  0.465                                     
B     0.50       14.41    11.77 0.450                                     
C     0.75       18.48    15.52 0.456                                     
D     1.00       21.15    17.51 0.453                                     
E     1.25       23.69    18.69 0.441                                     
F     1.50       26.10    19.88 0.432                                     
______________________________________                                    
 *Wt % data normalized based on throughput to allow easier data comparison

Example 4 (Comparative Example)

This example is a larger scale version of Example 1 where the addition rate of reagents was doubled to ascertain the ability of the catalyst to handle larger amounts of reactants on a per unit time basis. After quench and work-up, a product (104.91 g) was obtained6 which contained 23.3 weight % HMT (31.5 % molar yield based on 2,3-dimethyl-1-butene charged).

The results of the samplings are shown in Table B.

              TABLE B                                                     
______________________________________                                    
Wt % Analysis of Example 5 Samples*                                       
      Time of    Para-          HMT ÷ [Para-                          
Sample                                                                    
      Sample (hrs)                                                        
                 Cymene   HMT   Cymene + HMT]                             
______________________________________                                    
A     0.25       6.22     5.87  0.486                                     
B     0.50       15.86    9.36  0.371                                     
C     0.75       21.75    10.92 0.334                                     
D     1.00       27.74    12.17 0.305                                     
E     1.25       30.66    12.94 0.297                                     
F     1.50       32.54    13.07 0.287                                     
______________________________________                                    
 *Wt % data normalized based on throughput to allow easier data comparison

It is apparent from a comparison of the results of Examples 3 and 4 that without the phase transfer agent, the AlCl₃ catalyst cannot support the increased addition rate. Only in the initial moments of reaction does the comparative Example 4 compare in the rate to that of Example 3 with added phase transfer agent, an example of the process of the invention.

Various modifications of the invention in addition to those shown and described herein will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

Claims

What is claimed is:

1. A process for producing a polyalkyl tetrahydronaphthalene compound comprising contacting a partially substituted benzene compound, wherein said benzene compound is substituted with one or more substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction said substituents including at least one secondary alkyl group having only one alpha-hydrogen, and wherein said benzene compound is unsubstituted in at least one position adjacent to said secondary alkyl group, with an olefinic compound of the formula ##STR10## wherein R⁴, R⁵ and R⁶, independently, are substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction, provided that R⁵ and R⁶ are each other than H, in the presence of

an alkyl halide,

a Lewis acid, and

a phase transfer agent.

2. A process for producing a polyalkyl tetrahydronaphthalene compound of the Formulas ##STR11## comprising contacting a partially substituted benzene compound of the Formulas ##STR12## with an olefinic compound of the Formula ##STR13## in the presence of an alkyl halide,

a Lewis acid, and

a phase transfer agent,

wherein R¹, R², R³, R⁴, R⁵ and R⁶, independently, are substituents that do not substantially interfere with a Friedel-Crafts-type alkylation reaction, provided that R¹, R², R³, R⁵ and R⁶ are each other than H.

3. A process of claim 2 wherein

R⁴ is H, or a C₁ -C₃₀ straight chain, branched or cyclical alkyl; and

R¹, R², R³, R⁵ and R⁶, independently, are a C₁ -C₃₀ straight chain, branched or cyclical alkyl.

4. A process of claim 3 wherein said alkyl is a C₁ -C₅ alkyl.

5. A process of claim 3 wherein said alkyl i sa straight chain or branched alkyl.

6. A process of claim 3 wherein said polyalkyl tetrahydronaphthalene compound is of the Formula [I].

7. A process of claim 6 wherein

R⁴ is H or a C₁ -C₅ straight chain or branched alkyl; and

R¹, R², R³, R⁴, R⁵ and R⁶, independently, are a C₁ -C₅ straight chain or branched alkyl.

8. A process of claim 7 wherein

R¹, R², R³, R⁴, R⁵ and R⁶ are each methyl.

9. A process of claim 7 wherein

R¹ is ethyl; and

R², R³, R⁴, R⁵ and R⁶ are each methyl.

10. A process of claim 7 wherein

R¹ is n-propyl; and

R², R³, R⁴, R⁵ and R⁶ are each methyl.

11. A process of claim 7 wherein

R¹ is tertiary butyl; and

R², R³, R⁴, R⁵ and R⁶ are each methyl.

12. A process of claim 3 wherein said partially substituted benzene compound is of the Formula [IV].

13. A process of claim 12 wherein

R¹, R² and R³, independently, are a C₁ -C₅ straight chain or branched alkyl.

14. A process of claim 13 wherein

R¹, R² and R³ are each methyl.

15. A process of claim 13 wherein

R¹ is ethyl; and

R² and R³ are each methyl.

16. A process of claim 13 wherein

R¹ is n-propyl; and

R² and R³ are each methyl.

17. A process of claim 13 wherein

R¹ is tertiary-butyl; and

R² and R³ are each methyl.

18. A Process of claim 3 wherein

R⁴ is H or a C₁ -C₅ straight chain or branched alkyl; and

R⁵ and R⁶, independently, are a C₁ -C₅ straight chain or branched alkyl.

19. A process of claim 18 wherein

R⁴ is methyl.

20. A process of claim 18 wherein

R⁴, R⁵ and R⁶ are each methyl.

21. A process of claim 2 wherein said alkyl halide is selected from the group consisting of secondary alkyl halides, tertiary alkyl halides, propargyl halides and allyl halides.

22. A process of claim 21 wherein said alkyl halide is a tertiary alkyl halide selected from the group consisting of tertiary-butyl chloride, tertiary-amyl chloride, 2-methyl-2-chloropentane, 3-methyl-3-chloropentane, 1,8-dichloro-para-menthane and homologues thereof having fluorine, bromine or iodine atoms substituted for the chlorine atom.

23. A process of claim 22 wherein said tertiary alkyl halide is tertiary-butyl chloride.

24. A process of claim 2 wherein said Lewis acid is selected from the group consisting of metal halides, alkyl metal halides and alkyl metals.

25. A process of claim 24 wherein said Lewis acid is metal halide which is an aluminum halide.

26. A process of claim 25 wherein said aluminum halide is aluminum chloride.

27. A process of claim 2 wherein said phase transfer agent is selected from the group consisting of ammonium, phosphonium and sulfonium salts.

28. A process of claim 27 wherein said ammonium salt is a quaternary ammonium halide.

29. A process of claim 28 wherein said quaternary ammonium halide is methyltrioctylammonium chloride.

30. A process of claim 28 wherein said quaternary ammonium halide is a mixture of methyltrioctylammonium chloride and methyltridecylammonium chloride.

31. A process of claim 2 wherein said phase transfer agent is a tertiary amine compound substituted with hydrocarbons.

32. A process of claim 31 wherein said tertiary amine compound substituted hydrocarbons is trioctyl amine.

33. A process of claim 2 wherein said phase transfer agent and said Lewis acid are present in a molar ratio of less than 1 to 1, phase transfer agent to Lewis acid.

34. A process of claim 33 wherein said phase transfer agent and said Lewis acid are present in a molar ratio of about 0.5 to 1.0.

35. A process of claim 33 wherein said phase transfer agent is in an impure form and said phase transfer agent and said Lewis acid are present in a molar ratio of about 0.3 to 1.

36. A process of claim 2 further comprising a solvent.

37. A process of claim 36 wherein said solvent is selected from the group consisting of unhalogenated aliphatic, unhalogenated alicyclic and unhalogenated aromatic hydrocarbon solvents.

38. A process of claim 37 wherein said unhalogenated alicyclic solvent is cyclohexane.